Bimolecular nucleation methods for thermoplastics

ABSTRACT

Specific methods of inducing high nucleation rates in thermoplastics, such as polyolefins, and particularly, though not necessarily, polypropylenes, through the introduction of two different compounds that are substantially soluble within the target molten thermoplastic resin (such as, as one non-limiting example, an added compound including at least one acid group and an added organic salt) are provided. Such introduced components react to form a nucleating agent in situ within such a target molten thermoplastic resin which is then allowed to cool. Preferably, one compound is an acid, preferably bicyclic (i.e., two cyclic systems sharing at least three carbon atoms) or monocycloaliphatic (i.e., a single, saturated ring system) in nature, such as, without limitation, bicyclo[2.2.1]heptane dicarboxylic acid or hexahydrophthalic acid, and the other compound is an organic salt, such as a carboxylate, sulfonate, phosphate, oxalate, and the like, and more preferably selected from the group consisting of metal C 8 -C 22  esters. Such a production method thus provides a manner of generating in Situ the desired nucleating agent through reaction of such soluble compounds. Kits (e.g., masterbatch methods, for example) comprising such components for easy introduction within target molten polyolefin resins are also contemplated within this invention.

FIELD OF THE INVENTION

[0001] This invention relates to specific methods of inducing highnucleation rates in thermoplastics, such as polyolefins, andparticularly, though not necessarily, polypropylenes, through theintroduction of two different compounds that are substantially solublewithin the target molten thermoplastic resin (such as, as onenon-limiting example, an added compound including at least one acidgroup and an added organic salt). Such introduced components react toform a nucleating agent in situ within such a target moltenthermoplastic resin which is then allowed to cool. Preferably, onecompound is an acid, preferably bicyclic (i.e., two cyclic systemssharing at least three carbon atoms) or monocycloaliphatic (i.e., asingle, saturated ring system) in nature, such as, without limitation,bicyclo[2.2.1]heptane dicarboxylic acid or hexahydrophthalic acid, andthe other compound is an organic salt, such as a carboxylate, sulfonate,phosphate, oxalate, and the like, and more preferably selected from thegroup consisting of metal C₈-C₂₂ esters. Such a production method thusprovides a manner of generating in situ the desired nucleating agentthrough reaction of such soluble compounds. Kits (e.g., masterbatchmethods, for example) comprising such components for easy introductionwithin target molten polyolefin resins are also contemplated within thisinvention.

BACKGROUND OF THE PRIOR ART

[0002] All U.S. patents cited below are herein entirely incorporated byreference.

[0003] As used herein, the term “thermoplastic” is intended to mean apolymeric material that will melt upon exposure to sufficient heat butwill retain its solidified state, but not prior shape without use of amold or like article, upon sufficient cooling. Specifically, as well,such a term is intended solely to encompass polymers meeting such abroad definition that also exhibit either crystalline orsemi-crystalline morphology upon cooling after melt-formation throughthe use of the aforementioned mold or like article. Particular types ofpolymers contemplated within such a definition include, withoutlimitation, polyolefins (such as polyethylene, polypropylene,polybutylene, and any combination thereof), polyamides (such as nylon),polyurethanes, polyester (such as polyethylene terephthalate), and thelike (as well as any combinations thereof).

[0004] Thermoplastics have been utilized in a variety of end-useapplications, including storage containers, medical devices, foodpackages, plastic tubes and pipes, shelving units, and the like. Suchbase compositions, however, must exhibit certain physicalcharacteristics in order to permit widespread use. Specifically withinpolyolefins, for example, uniformity in arrangement of crystals uponcrystallization is a necessity to provide an effective, durable, andversatile polyolefin article. In order to achieve such desirablephysical properties, it has been known that certain compounds andcompositions provide nucleation sites for polyolefin crystal growthduring molding or fabrication. Generally, compositions containing suchnucleating compounds crystallize at a much faster rate than un-nucleatedpolyolefin. Such crystallization at higher temperatures results inreduced fabrication cycle times and a variety of improvements inphysical properties, such as, in one example, stiffness.

[0005] Such compounds and compositions that provide faster and or higherpolymer crystallization temperatures are thus popularly known asnucleators. Such compounds are, as their name suggests, utilized toprovide nucleation sites for crystal growth during cooling of athermoplastic molten formulation. Generally, the presence of suchnucleation sites results in a larger number of smaller crystals. As aresult of the smaller crystals formed therein, clarification of thetarget thermoplastic may also be achieved, although excellent clarity isnot always a result. The more uniform, and preferably smaller, thecrystal size, the less light is scattered. In such a manner, the clarityof the thermoplastic article itself can be improved. Thus, thermoplasticnucleator compounds are very important to the thermoplastic industry inorder to provide improved clarity, physical properties and/or fasterprocessing.

[0006] Dibenzylidene sorbitol compounds are common nucleator compounds,particularly for polypropylene end products. Compounds such as1,3-0-2,4-bis(3,4-dimethylbenzylidene) sorbitol (hereinafter DMDBS),available from Milliken Chemical under the trade name Millad® 3988,provide excellent nucleation characteristics for target polypropylenesand other polyolefins. Other well known compounds include sodiumbenzoate, sodium 2,2′-methylene-bis-(4,6-di-tert-butylphenyl) phosphate(from Asahi Denka Kogyo K.K., known as NA-11), talc, and the like.

[0007] Other acetals of sorbitol and xylitol are typical nucleators forpolyolefins and other thermoplastics as well. Dibenzylidene sorbitol(DBS) was first disclosed in U.S. Pat. No. 4,016,118 by Hamada, et al.as an effective nucleating and clarifying agents for polyolefins. Sincethen, large number of acetals of sorbitol and xylitol have beendisclosed. Representative US patents include: Kawai, et al., U.S. Pat.No. 4,314,039 on di(alkylbenzylidene) sorbitols; Mahaffey, Jr., U.S.Pat. No. 4,371,645 on di-acetals of sorbitol having at least onechlorine or bromine substituent; Kobayashi, et al., U.S. Pat. No.4,532,280 on di(methyl or ethyl substituted benzylidene) sorbitol;Rekers, U.S. Pat. No. 5,049,605 on bis(3,4-dialkylbenzylidene) sorbitolsincluding substituents forming a carbocyclic ring.

[0008] Other examples of effective nucleating agents are the metal saltsof organic acids. Wijga in U.S. Pat. Nos. 3,207,735, 3,207,736, and3,207,738, and Wales in U.S. Pat. Nos. 3,207,737 and 3,207,739, allpatented Sep. 21, 1966, suggest that aliphatic, cycloaliphatic, andaromatic carboxylic, dicarboxylic or higher polycarboxylic acids,corresponding anhydrides and metal salts are effective nucleating agentsfor polyolefin. They further state that benzoic acid type compounds, inparticular sodium benzoate, are the best embodiment of the nucleatingagents.

[0009] Another class of nucleating agents, alluded to above, wassuggested by Nakahara, et al. in U.S. Pat. No. 4,463,113, in whichcyclic bis-phenol phosphates were disclosed as nucleating and clarifyingagents for polyolefin resins. Kimura, et al. then suggests in U.S. Pat.No. 5,342,868 that the addition of an alkali metal carboxylate to basicpolyvalent metal salt of cyclic organophosphoric ester can furtherimprove the clarification effects of such additives. This patent thus atbest discloses the reaction of a salt with a base, although such areaction is never actually stated to occur within this reference.Compounds that are based upon these technologies are marketed under thetrade name NA-11 and NA-21.

[0010] U.S. Pat. Nos. 5,300,549 and 5,319,012, as well as published PCTApplication WO 01/53404 all disclose the addition of metal salts toacidic catalyst residues (i.e., aluminum catalyst by-products having lowpH levels, but no acid functionalities, such as carboxyl groups,thereon) already present within a target resin as a means to providenucleation and clarity to thermoplastics. None of these patentsdiscloses the ability to introduce separately to molten resins differentsoluble compounds therein to generate a bicyclic or monocycloaliphaticnucleating agent in situ.

[0011] U.S. Pat. No. 5,231,126 teaches beta-nucleation of polypropylenethrough the reaction of linear aliphatic or aromatic acids with oxides,hydroxides, or salts within target polypropylene. Such a method requiresspecific types of dibasic acids to accomplish the desiredbeta-polypropylene crystal generation at sufficiently high levels.Generally, however, the production of such high levels of beta-crystalsis unwanted and thus such beta-nucleation of target polypropylene is tobe avoided. In fact, in order to provide the best clarity in targetpolypropylene, the amount of beta-crystals should be at most 5% of thetotal amount of polypropylene crystals within the target plastic itself,with the closer to 0% beta-crystals the better for the best level of lowhaze (and thus a non-opaque result).

[0012] Furthermore, a certain class of bicyclic compounds, such asbicyclic dicarboxylic acid and salts, have been taught as polyolefinnucleating agents as well within Patent Cooperation Treaty ApplicationWO 98/29494, to Minnesota Mining and Manufacturing. The best workingexample of this technology is embodied in disodiumbicyclo[2.2.1]-5-heptene-2,3-dicarboxylate and formulations with suchcompounds.

[0013] Such compounds all impart relatively high polyolefincrystallization temperatures; however, each also exhibits its owndrawback for large-scale industrial applications.

[0014] For example, of great interest is the compatibility of suchcompounds with different additives widely used within typical polyolefin(e.g., polypropylene, polyethylene, and the like) plastic articles. Forinstance, calcium stearate is a very popular acid neutralizer presentwithin typical polypropylene formulations to protect the end productfrom catalyst residue attack. Unfortunately, most of the nucleatorcompounds noted above exhibit deleterious reactions with such compoundswithin polyolefin articles. For sodium, and other like metal ions, itappears that the calcium ion from the stearate transfers positions withthe sodium ions of the nucleating agents, rendering the nucleatingagents ineffective for their intended function. As a result, suchcompounds sometimes exhibit unwanted plate-out characteristics andoverall reduced nucleation performance (as measured, for example) by adecrease in crystallization temperature during and after polyolefinprocessing. Other processing problems are evident with such compounds aswell.

[0015] As noted above, beta-crystal polypropylene structures arepreferably avoided, with at most 5% in terms of total numbers ofpolypropylene crystals in the final article preferred. Suchbeta-crystals do generally aid with impact resistance and stiffness ofthe target polypropylene article; however, in terms of clarity, thepresence of above 5% is detrimental and such a small amount can causehigh degrees of unwanted opacity in target transparent resin articles.

[0016] Other problems encountered with the standard nucleators notedabove include inconsistent nucleation due to dispersion problems,resulting in stiffness and impact variation in the polyolefin article.Substantial uniformity in polyolefin production is highly desirablebecause it results in relatively uniform finished polyolefin articles.If the resultant article does not contain a well-dispersed nucleatingagent, the entire article itself may suffer from a lack of rigidity andlow impact strength. Thus, simplicity of production as well as effectivedispersion of the initial components (reactants) within the targetthermoplastic resin is needed, as well as effective nucleation thereby.

[0017] Furthermore, storage stability of nucleator compounds andcompositions is another potential problem with thermoplastic nucleatorsand thus is of enormous importance as well. Since nucleator compoundsare generally provided in powder or granular form to the polyolefinmanufacturer, and since uniform small particles of nucleating agents isimperative to provide the requisite uniform dispersion and performance,such compounds must remain as small particles through storage. Certainnucleators, such as sodium benzoate, exhibit high degrees ofhygroscopicity such that the powders made therefrom hydrate easilyresulting in particulate agglomeration. Such agglomerated particles mayrequire further milling or other processing for deagglomeration in orderto achieve the desired uniform dispersion within the targetthermoplastic. Furthermore, such unwanted agglomeration due to hydrationmay also cause feeding and/or handling problems for the user.

[0018] Also of great interest is the compatibility of such compoundswith different additives widely used within typical polyolefin (e.g.,polypropylene, polyethylene, and the like) plastic articles. As notedpreviously, calcium stearate compatibility is particularly important.Unfortunately, most of the nucleators compounds noted above (such assodium benzoate, NA-11, disodium bicyclo[2.2.1] heptene dicarboxylate)exhibit much deleterious nucleating efficacy with such compounds withinpolyolefin articles. In order to avoid combinations of these standardnucleators and calcium salts, other nonionic acid neutralizers, such asdihydrotalcite (DHT4-A), would be necessary for use in conjunction withsuch nucleators. Such a combination, however, has proven problematic incertain circumstances due to worsened aesthetic characteristics (e.g.,higher haze), and certainly higher costs in comparison with standardcalcium salts.

[0019] Some nucleating agents, such as certain DBS derivatives, exhibitcertain practical deficiencies such as a tendency to plate-out at highprocessing temperatures. DBS derivatives, particularly where thearomatic rings are mono-substituted, show much improved thermalstability. However, such compounds also tend to exhibit undesirablemigratory properties coupled with problematic organoleptic deficiencieswithin certain polyolefin articles. As a result, such compounds arelimited in their practical in some important areas, such as medicaldevice packaging.

[0020] These noticeable problems have thus created a long-felt need inthe polyolefin nucleator compound industry to provide such compoundsthat do not exhibit the aforementioned problems and provide excellentpeak crystallization temperatures for the target polyolefin themselves.To date, the best compounds for this purpose remain those noted above.Unfortunately, nucleators exhibiting exceptionally high peakcrystallization temperatures, low hygroscopicity, excellent thermalstability, and non-migratory properties within certain targetpolyolefin, and compatibility with most standard polyolefin additives(such as, most importantly, calcium stearate) have not been developedwithin the polyolefin nucleator industry.

[0021] Furthermore, methods of utilizing the benefits of typical saltadditives within thermoplastics and polyolefins have heretofore beenunexplored. In such a potential scenario, the ability to react addedsalts, such as acid scavengers, with nucleator precursor compounds couldpossibly provide, in situ, the desired type and amount of ultimatenucleating agent within the target thermoplastic resin. To date therehas been no teaching of the viability of providing nucleation ofthermoplastics (preferably polyolefins, more preferably polypropylene ofvery low beta-crystal levels) through the reaction of added bicyclic ormonocycloaliphatic components (preferably, though not necessarily acidsof such types) with added organic acids. Again, the closest artdiscloses either the production of high beta-crystal polypropylenelevels, reactions between organic salts and bases, or the introductionof organic salts to already-present catalyst residues within targetthermoplastics. Such an in situ reaction between added components couldpotentially reduce cost through supplying the needed metal ions from thealready-present salts, as well as through simplification of the overallreaction itself through improved dispersion of the initially addedcompounds. Such a situation could be beneficial, for example, if thenucleator precursor exhibits better stability or other characteristicprior to introduction within target thermoplastic, as compared with thedesired ultimate nucleating agent. However, again, no such teaching orfair suggestion has been presented within the pertinent prior art ofthis specific potential reaction.

OBJECTS OF THE INVENTION

[0022] Therefore, an object of the invention is to provide athermoplastic (e.g., without limitation, polyolefin) nucleating agentthat exhibits exceptional nucleation efficacy as indicated byexceptional high polymer peak crystallization temperatures which can begenerated in situ within the target thermoplastics and exhibiting as lowan amount of beta-crystal polypropylene structures as possible. Afurther object of the invention is to provide a simple method ofnucleating thermoplastics utilizing a commonly added metal salt compoundas a component to provide a metal ion needed for formation of thedesired nucleating agent in reaction with an added compound solublewithin the target molten thermoplastic resin, such as, as onenon-limiting example, an acid (preferably, though not necessarily, adiacid). Yet another object of this invention is to provide nucleatingand possibly clarifying compounds and compositions generated in situ asnoted above that exhibit exceptional thermal stability and non-migratoryproperties. Yet another object of the invention is to provide such insitu generated nucleating compounds that provide excellent mechanicalproperties within the target thermoplastics. Additionally, it is anobject of this invention to provide such in situ generated nucleatingcompounds or compositions that may be used in various polyolefin mediafor myriad end-uses.

[0023] Accordingly, this invention encompasses a method of nucleating athermoplastic formulation comprising the steps of

[0024] a) providing a molten thermoplastic formulation;

[0025] b) introducing, either simultaneously or separately, at least onebicyclic compound or monocycloaliphatic compound that exhibitssubstantial solubility within said formulation of step “a” and at leastone organic salt (in order to generate, as one non-limiting example, abicyclic monocycloaliphatic nucleating agent in situ); and

[0026] c) allowing the resultant mixture in step “b” to cool to form anucleated thermoplastic article; wherein the resultant thermoplasticcomprises at most 5% in total parts of beta-crystals of polypropylene,and wherein said nucleated thermoplastic article exhibits acrystallization temperature in excess of that or the same thermoplasticfree from any nucleating agents therein.

[0027] Preferably, without limitation, such an inventive method ofnucleating a thermoplastic formulation comprising the steps of

[0028] a) providing a molten thermoplastic formulation;

[0029] b) introducing, either simultaneously or separately, at least onecompound conforming with either of formulae (I) or (II)

[0030] wherein wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ areeither the same or different and are individually selected from thegroup consisting of hydrogen, C₁-C₉ alkyl [wherein any two vicinal(neighboring) or geminal (same carbon) alkyl groups may be combined toform a carbocyclic ring of up to six carbon atoms], hydroxy, C₁-C₉alkoxy, C₁-C₉ alkyleneoxy, amine, and C₁-C₉ alkylamine, halogens(fluorine, chlorine, bromine, and iodine), and phenyl, wherein geminalconstituents may be the same except that such geminal constituentscannot simultaneously be hydroxy; and wherein geminal constituents maybe different from each other, except that such geminal constituents maynot be hydroxy and halogen or hydroxy and amine simultaneously (whereinthe carboxylates may be cis or trans, with cis preferred for nucleationcapabilities);

[0031] wherein R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, and R₂₀ areindividually selected from the group consisting of hydrogen, C₁-C₉alkyl, hydroxy, C₁-C₉ alkoxy, C₁-C₉ alkyleneoxy, amine, and C₁-C₉alkylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal C₁-C₉carbocyclic, wherein geminal constituents may be the same except thatsuch geminal constituents cannot simultaneously be hydroxy; and whereingeminal constituents may be different from each other, except that suchgeminal constituents may not be hydroxy and halogen or hydroxy and aminesimultaneously; wherein at least one of R′ and R″ is eitherC(O)—NR₂₁C(O) or C(O)O—R′″, wherein R₂₁ is selected from the groupconsisting of C₁-C₃₀ alkyl, hydrogen, C₁-C₃₀ alkoxy, and C₁-C₃₀polyoxyalkyl, and wherein if R′ and R″ are both C(O)O—R′″, then at leastone R′″ for either R′ or R″ must be H, and at most one R′″ for either R′or R″ is a metal cation (such as monovalent metals sodium, potassium,and the like). Furthermore, for Formula II, in each of these potentialcompounds, the stereochemistry at the metal carboxylates may be cis ortrans, although cis is preferred. In Formula II, the stereochemistry atthe R′ and R″ groups may be cis-exo, cis-endo, or trans, althoughcis-endo is preferred.

[0032] The preferred embodiment polyolefin articles and additivecompositions for polyolefin formulations comprising at least one of suchcompounds, broadly stated as saturated bicyclic carboxylic acids, arealso encompassed within this invention.

[0033] The term “bicyclic” is intended to encompass compounds with atleast two cyclic moieties that share at least 3 carbon atoms. This termmay include unsaturated as well as saturated systems, although saturatedtypes [such as in Formula (II)] are preferred.

[0034] The term “monocycloaliphatic” is intended to encompass compoundswith a single saturated ring system therein. Non-limiting preferredexamples of Formula (I) compounds include hexahydrophthalic acid andmethyl-substituted hexahydrophthalic acid. Such compounds are saturatedin nature and exhibit relatively high crystallization temperatures inthermoplastics, although to a less effective level than those preferredcompounds conforming to Formula (II), above.

[0035] The term “organic salts” is intended to encompass any type ofsalt with an organic component therein and thus does not include metalhalides (such as sodium chloride, aluminum chloride, potassium bromide,and the like). Such added organic salts must be able to thoroughlydisperse within the target thermoplastic in order to effectuate properdissociation between the cation portion (such as metal ions, ammoniumions, and the like) and the organic anion (such as, without limitation,and only as possible types, carboxylates, sulfonates, oxalates,phosphates, and the like). Furthermore, poly salts may be utilized aswell [with either multiple metal ions present or multiple anions per asingle metal ion, such as, again, without limitation, poly(sodiumacrylate)]. As noted above, the solubility of such an organic salt, aswell as its propensity to easily dissociate in order to contribute thenecessary cation to displace the hydrogen on the acid compound whilethoroughly dispersed within the target thermoplastic are of utmostnecessity in this situation. The presence of highly oxidative halideanions is typically detrimental to the function of the desiredthermoplastic and can discolor or actually deleteriously affect thestability and integrity of the finished thermoplastic, if not preventachieving a finished thermoplastic at all. Thus, the presence of organicacids, including anions such as C₈-C₂₂ esters, are important to permitproper in situ nucleator generation and simultaneous ability to producea desired and stable thermoplastic article. Additionally, some organicacids (calcium stearate, for example) are typically and commonly addedto thermoplastics (polyolefins, for example) for acid scavengingpurposes. Thus, such needed organic salts are compatible with suchthermoplastics as well and should not deleteriously react with anyadditives present within the target molten resin or finished article.Preferred examples of such organic salts include, without limitation,calcium stearate, sodium stearate, lithium stearate, and the like.

[0036] The term “substantial solubility” is intended to encompass atleast a degree of solubility such that upon introduction of an amountequal by weight to 1% of the target molten thermoplastic formulation, ata temperature of from 100-150° C., with a minimal amount of mixing(e.g., shear forces of at most ------- for --- seconds), the majority ofsolid particles added thereto become nonvisible. Preferably, completesolubility is met by this definition, although a lesser degree ofsolubility to the level noted above, is acceptable as well.

[0037] Furthermore, other nucleating agents, such as those noted aboveas within the prior art, may also be present if desired to providesimilar or different nucleation and/or clarifying capabilities withinthe target thermoplastic.

DETAILED DESCRIPTION OF THE INVENTION

[0038] As noted above, in order to develop a proper polyolefin nucleatorcompound or composition for industrial applications, a number ofimportant criteria needed to be met. The inventive methods meet all ofthese important requirements very well in particular by producing insitu compounds that act as excellent nucleating agents through thereaction of the preferred, non-limiting, compounds of either Formula (I)or (II) with the cations provided by the organic salts (carboxylates,for example). Thus, as one example, the presence of sufficient amountsof calcium stearate with the bicyclic acids of Formula (II), producecalcium bicyclic salts which are excellent nucleating agents for targetthermoplastics (sodium stearate thus produces disodium bicyclic salts,as another non-limiting example), preferably, though not necessarily,polyolefins, in particular, polypropylenes. Such bicyclic salts provideexcellent high peak crystallization temperatures in a variety ofpolyolefin formulations, particularly within random copolymerpolypropylene (hereinafter RCP) and homopolymer polypropylene(hereinafter HP). As a result, such inventive salts provide excellentmechanical properties for polyolefin articles without the need for extrafillers and rigidifying additives, and desirable processingcharacteristics such as improved (shorter) cycle time. Lastly, suchinventive salts do not interact deleteriously with such organic salts,including common polypropylene additives such as calcium stearate.

[0039] Such properties of the preferred in situ generated saturatedbicyclic nucleators are highly unexpected and unpredictable,particularly in view of the closest prior art, the WO 98/29494 referencediscloses nucleation and clarification additives for polyolefin articlesincluding unsaturated [2.2.1] dicarboxylate salts; however, there is noexemplification of a saturated dicarboxylate salt of this insitu-generated type as above. The closest embodiment within that art isidentified as disodium bicyclo[2.2.1]-5-heptene-2,3-dicarboxylate;nothing remotely discusses the method of forming in situ saturateddicarboxylate bicyclic salts through the co-introducing of bicyclicdiacids (or half-acids) with sufficient amounts of metal carboxylatesalts to produce the saturated bicyclic salts needed to induce highnucleation rates. In comparison, at least very least, it has beendetermined that, quite unexpectedly, the hydrogenation of theaforementioned unsaturated bicyclic compounds provides vastly improvednucleation efficacy. For this invention, then, the ability to generatesuch saturated bicyclic salts is again heretofore been unknown and thusprovides an unexpectedly efficacious nucleation capability. Furthermore,although unsaturated bicyclic compounds are taught by the referenceabove, there is no teaching or fair suggestion of the in situ generationof such compounds within target thermoplastics for nucleation purposes.As such, the ability to generate such compounds are thus encompassedwithin this invention as well, as the term “bicyclic” is not limited tothe preferred saturated species.

[0040] As indicated in Experimental Table 1, below, the peakcrystallization temperatures provided target polyolefin articles withthese inventive saturated compounds are from about 2.5 to about 5° C.above that for the related unsaturated compounds. Such dramaticimprovements are simply unexpected and are unpredictable from any knownempirical or theoretical considerations. Furthermore, significantimprovements in hygroscopicity of the saturated compounds were alsounexpectedly observed. Such unpredictable improvements are of greatpractical significance as discussed before.

[0041] Furthermore, masterbatching operations have heretofore beenextremely difficult, if not unavailable, for insoluble nucleation agentswithin thermoplastics due to dispersion problems and the consequentialgeneration of unsightly and undesirable swirls within the targetarticle. Furthermore, the amount of such insoluble nucleation agents hasnecessarily been very high due to a lack of efficiency of the desiredinsoluble nucleator in masterbatching methods; too much is unused orlost during the procedure to make it econically feasible. It has nowbeen found that the inventive method may be practiced by including athermoplastic-soluble acid component in a formulation separate from thatof a thermoplastic-soluble organic salt component. Such formulations,which may be present as powders, pellets, or liquids, or one may be inone form and the other in any other form, should also comprise at leastone polymer constituent as well. In this manner, for example, individualpellets of each formulation may be eventually combined within the targetmolten resin to provide desired nucleation characteristics. The resultsof such a masterbatching exercise have been quite unexpected because ofthe efficiency of the in situ generated nucleator and the highcrystallization temperatures accorded the target thermoplastic whileusing appreciably low levels of reactant additives for such a purpose.

[0042] Yet another surprise was the improved compatibility between theseacids as well as the generated preferred hexahydrophthalic acid salt andmore preferred saturated bicyclic salt nucleating agents and typicalacid scavenger salt compounds utilized within polyolefin formulationsand articles, such as calcium and lithium stearate. Of course, as notedabove, such stearates are preferable metal carboxylate salts that donatethe needed metal ions to the acid compounds to form the desired bicyclicsalts. However, once produced, the bicyclic salts exhibit compatibilitywith any excess acid scavengers remaining within the target resins aswell. This property, coupled with the high peak crystallizationtemperatures available from the inventive compounds, thus provides ahighly desirable thermoplastic nucleator compound that can be generatedin situ unexpectedly and surprisingly.

[0043] The needed acids are thus added within the target polyolefin inan amount from about 50 ppm to about 20,000 ppm by weight in order toprovide the aforementioned beneficial characteristics, most preferablyfrom about 200 to about 10000 ppm. Higher levels, e.g., 5-50% or more byweight, may also be used in a masterbatch formulation. Optionaladditives within either the precursor formulations (such as pellets,liquids, powders, etc. of the acid), or the masterbatch formulations, oreven within the final polyolefin article made therewith, may includeplasticizers, antistatic agents, stabilizers, ultraviolet absorbers, andother similar standard polyolefin thermoplastic additives. Otheradditives may also be present within this composition, most notablyplasticizers, acid scavengers, antimicrobials (preferably silver-basedion-exchange compounds, such as ALPHASAN® antimicrobials available fromMilliken & Company), antioxidants, flame retardants, light stabilizers,antistatic agents, colorants, pigments, perfumes, chlorine scavengers,and the like.

[0044] The organic salts that donate the needed cations (metal ions, forexample) to the acids are thus of any type that can also react with thedissociated hydrogens from the acids upon cation interaction and producea very weak acid that does not interfere with the production of thedesired thermoplastic itself (e.g., either is substantially inert andthus does not appreciably react with anything within the finished resinto any detrimental degree, or is easily removed through volatilization,blooming, or any other manner). Thus, broadly stated, the anion of themetal salt should exhibit a relatively high molecular weight and verylow oxidation capability. Preferably, such metal salts are metalcarboxylates, more preferably C₈-C₂₂ metal carboxylates. The metals arepreferably Group I and Group II metals, although other metal species,such as any of the transition metals (silver, aluminum, and the like)may also be present. More preferably, such metal carboxylates areselected from the group consisting of calcium stearate, sodium stearate,and lithium stearate. Such salts should be added in an amount at leastsufficient to impart the desired in situ generation of the necessarynucleating salt compound in tandem with the acid noted above. Also, forcompounds such as calcium stearate and lithium stearate, as examples,the amount present may include that necessary to impart the simultaneousproperties of acid scavenging within the target thermoplastic resin.Thus, from about 500 to about 15000 ppm are acceptable. More preferably,such a range is from about 750 to about 10000 ppm, most preferablybetween about 1000 and 5000 ppm.

[0045] The inventive additives thus form, in tandem with the requiredmetal salts, nucleating agents that are salts themselves. Preferably,such in situ generated salts conform with the structure of Formula (III)

[0046] wherein M1 and M2 are either the same or different, or arecombined to form a single metal atom, and are selected from the groupconsisting of metal and organic cations, and wherein R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, R₉, and R₁₀ are individually selected from the groupconsisting of hydrogen, C₁-C₉ alkyl, hydroxy, C₁-C₉ alkoxy, C₁-C₉alkyleneoxy, amine, C₁-C₉ alkylamine, halogen, phenyl, alkylphenyl, andgeminal or vicinal C₁-C₉ carbocyclic; and a second formulation comprisesat least one metal carboxylate salt. It is this generated compound thatprovides the most profound nucleation effects within the targetthermoplastic, although some residual acid may also exhibit a certaindegree of nucleation efficacy as well.

[0047] The term polyolefin or polyolefin resin is intended to encompassany materials comprised of at least one polyolefin compound. Preferredexamples include isotactic and syndiotactic polypropylene, polyethylene,poly(4-methyl)pentene, polybutylene, and any blends or copolymersthereof, whether high or low density in composition. The polyolefinpolymers of the present invention may include aliphatic polyolefins andcopolymers made from at least one aliphatic olefin and one or moreethylenically unsaturated co-monomers. Generally, the co-monomers, ifpresent, will be provided in a minor amount, e.g., about 10 percent orless or even about 5 percent or less, based upon the weight of thepolyolefin (e.g. random copolymer polypropylene), but copolymerscontaining up to 25% or more of the co-monomer (e.g., impact copolymers)are also envisaged. Other polymers or rubber (such as EPDM or EPR) mayalso be compounded with the polyolefin to obtain the aforementionedcharacteristics. Such co-monomers may serve to assist in clarityimprovement of the polyolefin, or they may function to improve otherproperties of the polymer. Other examples include acrylic acid and vinylacetate, etc. Examples of olefin polymers whose transparency can beimproved conveniently according to the present invention are polymersand copolymers of aliphatic monoolefins containing 2 to about 6 carbonatoms which have an average molecular weight of from about 10,000 toabout 2,000,000, preferably from about 30,000 to about 300,000, such as,without limitation, polyethylene, linear low density polyethylene,isotactic polypropylene, syndiotactic polypropylene, crystallineethylenepropylene copolymer, poly(1-butene), polymethylpentene,poly(1-hexene), poly(1-octene), and polyvinyl cyclohexane. Thepolyolefins of the present invention may be described as linear, regularpolymers that may optionally contain side chains such as are found, forinstance, in conventional low density polyethylene.

[0048] Although polyolefins are preferred, the nucleating agents of thepresent invention are not restricted to polyolefins, and may also givebeneficial nucleation properties to polyesters such as polyethyleneterephthalate (PET), polybutylene terephthalate (PBT), and polyethylenenaphthalate (PEN), as well as polyamides such as Nylon 6, Nylon 6,6, andothers. Generally, any thermoplastic composition having some crystallinecontent may be improved with the nucleating agents of the presentinvention.

[0049] The inventive method may also be practiced through theintroduction of an additive composition comprising both the needed acidand metal salt components within a molten target thermoplastic resin andallowing the resin to cool into a desired article (through molding,extrusion, and the like). Such additive compositions may be present inany standard additive form, including, without limitation, powder,prill, agglomerate, liquid suspension, and the like, particularlycomprising dispersion aids such as polyolefin (e.g., polyethylene)waxes, stearate esters of glycerin, montan waxes, mineral oil, and thelike. Basically, any form may be exhibited by such a combination orcomposition including such combination made from blending,agglomeration, compaction, and/or extrusion.

[0050] The composition may then be processed and fabricated by anynumber of different techniques, including, without limitation, injectionmolding, injection blow molding, injection stretch blow molding,injection rotational molding, extrusion, extrusion blow molding, sheetextrusion, film extrusion, cast film extrusion, foam extrusion,thermoforming (such as into films, blown-films, biaxially orientedfilms), thin wall injection molding, and the like into a fabricatedarticle.

PREFERRED EMBODIMENTS OF THE INVENTION

[0051] This invention can be further elucidated through the followingexamples where examples of particularly preferred embodiment within thescope of the present invention are presented.

[0052] Production of Inventive Additive Compositions

[0053] The preferred additive compositions were produced in accordancewith the following table (formulations 5 and 6 were separate made formasterbatching): TABLE 1 Acid/Salt Combinations and Amounts Added Ex. #Acid (ppm) Salt (ppm) 1 bicyclo[2.2.1]heptane-2,3-dicarboxylicCaStearate (6600 ppm) acid (1800 ppm) 2 same NaStearate (6700 ppm) 3same LiStearate (6400 ppm) 4 same ZnStearate (7000 ppm) 5 same (but at83000 ppm) — 6 — CaStearate (273200 ppm) 7 hexahydrophthalic acid (2500ppm) LiStearate (1000 ppm) 8 same CaStearate (1000 ppm) 9endo-norbornene-2,3-dicarboxylic acid NaStearate (3400 ppm) (1000 ppm)

[0054] Each example formulation was pelletized with a polypropylenehomopolymer or random copolymer (for examples 7 and 8) for furtherintroduction within the target thermoplastics (polypropylenes) as notedbelow. These samples were then compared with commercial samples ofMillad® 3988, sodium benzoate, NA-11, and NA-21, as well as alreadyprepared unsaturated bicyclic compounds.

[0055] Nucleation Efficacy Test:

[0056] Thermoplastic compositions (plaques) were produced comprising theadditives from the Examples above and sample homopolymer polypropylene(HP) resin plaques or sample random copolymer polypropylene (RCP) resinplaques, produced dry blended, extruded through a single screw extruderat 400-450° F., and subsequently pelletized. Accordingly, one kilogrambatches of target polypropylene were produced in accordance with thefollowing tables: HOMOPOLYMER POLYPROPYLENE COMPOSITION TABLE 1Component Amount Polypropylene homopolymer (Himont Profax ® 6501) 1000 gIrganox ® 1010, Primary Antioxidant (from Ciba)  500 ppm Irgafos ® 168,Secondary Antioxidant (from Ciba) 1000 ppm Inventive Nucleator (fromTable I) as noted

[0057] HOMOPOLYMER POLYPROPYLENE COMPOSITION TABLE 2 Component AmountPolypropylene homopolymer (Himont Profax ® 6301) 1000 g Irganox ® 1010,Primary Antioxidant (from Ciba)  500 ppm Irgafos ® 168, SecondaryAntioxidant (from Ciba) 1000 ppm Inventive Nucleator (from Table I) asnoted

[0058] RANDOM COPOLYMER POLYPROPYLENE COMPOSITION TABLE Component AmountPolypropylene random copolymer flake (3% ethylene) 1,000 g Irganox ®1010, Primary Antioxidant (from Ciba)   500 ppm Irgafos ® 168, SecondaryAntioxidant (from Ciba)  1000 ppm Inventive Nucleator (from Table I) asnoted

[0059] The base HP or RCP and all additives were weighed and thenblended in a Papenmeier (Welex) mixer for 1 minute at about 1600 rpm.All samples were then melt compounded on a Killion single screw extruderat a ramped temperature from about 204° to 232° C. through four heatingzones. The melt temperature upon exit of the extruder die was about 246°C. The screw had a diameter of 2.54 cm and a length/diameter ratio of24:1. Plaques of formulations 1-4 and 7-9, from above, were then madethrough extrusion into an Arburg 25 ton injection molder. The molder wasset at a temperature anywhere between 190 and 260° C., with a range of190 to 240° C. preferred, most preferably from about 200 to 230° C. Theplaques had dimensions of about 51 mm×76 mm×1.27 mm, and the mold had amirror finish which was transferred to the individual plaques. The moldcooling circulating water was controlled at a temperature of about 25°C. Formulations 5 and 6 (masterbatch) were directly let down at theappropriate ratio (preferably, 40:1 of concentrate to base resinpellets) into the molder for manufacture of the test piece as describedabove.

[0060] Testing for nucleating effects and other important criteria wereaccomplished through the formation of plaques of clarified polypropylenethermoplastic resin. These plaques were formed through the processoutlined above with the specific compositions listed above in Table 1.

[0061] These plaque formulations are, of course, merely preferredembodiments of the inventive article and method and are not intended tolimit the scope of this invention. The resultant plaques were thentested for peak crystallization temperatures (by Differential ScanningCalorimetry). Crystallization is important in order to determine thetime needed to form a solid article from the molten polyolefincomposition. Generally, a polyolefin such as polypropylene has acrystallization temperature of about 110° C. at a cooling rate of 20°C./min. In order to reduce the amount of time needed to form the finalproduct, as well as to provide the most effective nucleation for thepolyolefin, the best nucleator compound added will invariably alsoprovide the highest crystallization temperature for the final polyolefinproduct. The nucleation composition efficacy, particular polymer peakcrystallization temperature (T_(c)), was evaluated by using DSCaccording to ASTM D-794-85 with a modified cooling rate of 20°C./minute. To measure these temperatures, the specific polypropylenecomposition was heated from 60° C. to 220° C. at a rate of 20° C. perminute to produce a molten formulation and held at the peak temperaturefor 2 minutes. At that time, the temperature was then lowered at a rateof 20° C. per minute until it reached the starting temperature of 60° C.The crystallization temperature was thus measured as the peak maximumduring the crystallization exotherm. The clarification performance ofthe nucleators was measured using ASTM D 1003-92.

[0062] The following Table lists the peak crystallization temperaturesfor the plaques prepared above: EXPERIMENTAL TABLE 1 Performance ofAdditives Nucleator Precursors in Polypropylene Homopolymer FinalAdditive Polym. Cryst. Additives Conc. (ppm) Temp % Haze Ex. 1 2300125.7 21% Ex. 2 2300 123.7 35% Ex. 3 2300 119.7 37% Ex. 4 2300 121.4 39%Exs. 5 and 6 (Masterbatch) 5000 125.1 33% Ex. 7 2500 113.5 28% Ex. 82500 111.9 28% Ex. 9 4400 116.3 71% None — 110 68% Disodium 1000 122 50%bicyclo[2.2.1]heptene dicarboxylate Disodium 2500 123 46%bicyclo[2.2.1]heptene dicarboxylate DMDBS 2500 123 11% NA-11 1000 12432% NA-21 2500 123 20%

[0063] When introduced within the target resins, the inventive exampleformulations easily dissolved therein such that no solids weredetectable visibly with the naked eye. Thus, the added compounds, beingsolids originally, were substantially soluble within the target resins.

[0064] The data show that the inventive additives at least exhibitacceptable crystallization temperatures, and at most, bettercrystallization temperatures than the comparative typical nucleatingagents (and, in some cases, lower haze measurements as well)(Formulation4 is tested within the Homopolymer Polypropylene Composition 2, fromabove, while the remaining tests for Examples 1-3, and 5-6, as well asthe comparative data were undertaken within Homopolymer PolypropyleneComposition 1; Examples 7-9 were present within RCP).

[0065] Each resultant inventive polypropylene was then analyzed forbeta-crystal presence. The beta-PP (crystal) content was evaluated byusing a Perkin-Elmer DSC7 (although an equivalent type of DSC could beused as well). To measure % beta-PP, the specific polypropylenecomposition was heated from 60° C. to 220° C. at a rate of 20° C. perminute in order to completely melt the polymer. When PP is analyzedunder these conditions, alpha-PP crystals melt with a melting peaktemperature of about 165° C., while beta-PP crystals melt with a meltingpeak temperature much less than 165° C., typically 148° C. The absenceof lower melting peak at about 148° C. indicates a beta-PP (crystal)content of less than 5%. When a separate peak having a melting peaktemperature of about 148° C. is identified, the beta content can bequantified. The % beta-PP can then be determined by dividing the heat offusion of the beta-PP peak by the heat of fusion of all of the PPcrystals in the sample (the total heat of fusion of the polymer). Inactuality, the heat of fusion of beta-PP crystals is slightly lower thanthe heat of fusion of alpha-PP crystals. Thus, the test noted above issimplified to a certain extent such that a reading of 6% beta-PPcrystals may actually be calculated to be 5%. For the inventive resinsdiscussed and exemplified above, however, there were no melting peaktemperatures indicating beta-PP crystal presence (at about 148° C.).Thus, no detection of such beta-PP structures was measured (and thusthey all exhibited less than 5% beta-PP crystals).

[0066] Having described the invention in detail it is obvious that oneskilled in the art will be able to make variations and modificationsthereto without departing from the scope of the present invention.Accordingly, the scope of the present invention should be determinedonly by the claims appended hereto.

That which is claimed is:
 1. A method of nucleating a thermoplasticformulation comprising the steps of a) providing a molten thermoplasticformulation; b) introducing, either simultaneously or separately, atleast one compound substantially soluble within said formulation of step“a” selected from the group consisting of at least one bicyclic compoundand at least one monocycloaliphatic compound, and at least one organicsalt; and c) allowing the resultant mixture in step “b” to cool to forma nucleated thermoplastic article; wherein said nucleated thermoplasticarticle exhibits a peak crystallization temperature in excess of thatfor the same thermoplastic free from any nucleation agent therein. 2.The method of claim 1 wherein said thermoplastic formulation comprisesat least one polyolefin.
 3. The method of claim 2 wherein said at leastone polyolefin is polypropylene.
 4. The method of claim 1 wherein saidadded compounds of step “b” are added simultaneously within said moltenthermoplastic formulation of step “a”.
 5. A method of nucleating athermoplastic formulation comprising the steps of a) providing a moltenthermoplastic formulation; b) introducing, either simultaneously orseparately, at least one compound conforming with either of formulae (I)or (II)

wherein wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are eitherthe same or different and are individually selected from the groupconsisting of hydrogen, C₁-C₉ alkyl [wherein any two vicinal(neighboring) or geminal (same carbon) alkyl groups may be combined toform a carbocyclic ring of up to six carbon atoms], hydroxy, C₁-C₉alkoxy, C₁-C₉ alkyleneoxy, amine, and C₁-C₉ alkylamine, halogens(fluorine, chlorine, bromine, and iodine), and phenyl, wherein geminalconstituents may be the same except that such geminal constituentscannot simultaneously be hydroxy; and wherein geminal constituents maybe different from each other, except that such geminal constituents maynot be hydroxy and halogen or hydroxy and amine simultaneously;

wherein R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, and R₂₀ areindividually selected from the group consisting of hydrogen, C₁-C₉alkyl, hydroxy, C₁-C₉ alkoxy, C₁-C₉ alkyleneoxy, amine, and C₁-C₉alkylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal C₁-C₉carbocyclic, wherein geminal constituents may be the same except thatsuch geminal constituents cannot simultaneously be hydroxy; and whereingeminal constituents may be different from each other, except that suchgeminal constituents may not be hydroxy and halogen or hydroxy and aminesimultaneously; wherein at least one of R′ and R″ is eitherC(O)—NR₂₁C(O) or C(O)O—R′″, wherein R₂₁ is selected from the groupconsisting of C₁-C₃₀ alkyl, hydrogen, C₁-C₃₀ alkoxy, and C₁-C₃₀polyoxyalkyl, and wherein if R′ and R″ are both C(O)O—R′″, then at leastone R′″ for either R′ or R″ must be H, and at most one R′″ for either R′or R″ is a metal cation; and at least one organic salt; and c) allowingthe resultant mixture in step “b” to cool.
 6. The method of claim 5wherein said acid compound conforms with Formula (II).
 7. The method ofclaim 6 wherein said thermoplastic formulation comprises at least onepolyolefin.
 8. The method of claim 7 wherein said at least onepolyolefin is polypropylene.
 9. The method of claim 5 wherein said atleast one acid compound and said at least one organic salt of step “b”are added simultaneously within said molten thermoplastic formulation ofstep “a”.
 10. The method of claim 5 wherein said at least one compoundconforming to the structure of Formula (I) and said at least one organicsalt of step “b” are added simultaneously within said moltenthermoplastic formulation of step “a”.
 12. The method of claim 5 whereinsaid at least one compound conforming to the structure of Formula (II)and said at least one organic salt of step “b” are added simultaneouslywithin said molten thermoplastic formulation of step “a”.
 13. A methodof nucleating a thermoplastic formulation comprising the steps of a)providing a molten thermoplastic formulation; c) adding at least twocomponents which, upon reacting together, generate in situ a bicyclicnucleating therein said thermoplastic formulation; and c) allowing theresultant mixture in step “b” to cool.
 14. The method of claim 14wherein said thermoplastic formulation comprises at least onepolyolefin.
 15. The method of claim 15 wherein said at least onepolyolefin is polypropylene.
 16. A method of nucleating a thermoplasticformulation comprising the steps of a) providing a molten thermoplasticformulation; d) adding at least two different components which, uponreacting together, generate in situ, a monocycloaliphatic nucleatingtherein said thermoplastic formulation; and c) allowing the resultantmixture in step “b” to cool.
 17. The method of claim 16 wherein saidthermoplastic formulation comprises at least one polyolefin.
 18. Themethod of claim 17 wherein said at least one polyolefin ispolypropylene.
 19. A polymer additive composition comprising at leastone compound substantially soluble within molten polypropylene selectedfrom the group consisting of at least one bicyclic compound and at leastone monocycloaliphatic compound.
 20. The polymer additive composition ofclaim 19 wherein said at least one monocycloaliphatic compound conformsto the structure of Formula (I):

wherein wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are eitherthe same or different and are individually selected from the groupconsisting of hydrogen, C₁-C₉ alkyl [wherein any two vicinal(neighboring) or geminal (same carbon) alkyl groups may be combined toform a carbocyclic ring of up to six carbon atoms], hydroxy, C₁-C₉alkoxy, C₁-C₉ alkyleneoxy, amine, and C₁-C₉ alkylamine, halogens(fluorine, chlorine, bromine, and iodine), and phenyl, wherein geminalconstituents may be the same except that such geminal constituentscannot simultaneously be hydroxy; and wherein geminal constituents maybe different from each other, except that such geminal constituents maynot be hydroxy and halogen or hydroxy and amine simultaneously.
 21. Thepolymer additive composition of claim 19 wherein said at least onemonocycloaliphatic compound conforms to the structure of Formula (II):

wherein R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, and R₂₀ areindividually selected from the group consisting of hydrogen, C₁-C₉alkyl, hydroxy, C₁-C₉ alkoxy, C₁-C₉ alkyleneoxy, amine, and C₁-C₉alkylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal C₁-C₉carbocyclic, wherein geminal constituents may be the same except thatsuch geminal constituents cannot simultaneously be hydroxy; and whereingeminal constituents may be different from each other, except that suchgeminal constituents may not be hydroxy and halogen or hydroxy and aminesimultaneously; wherein at least one of R′ and R″ is eitherC(O)—NR₂₁C(O) or C(O)O—R′″, wherein R₂₁ is selected from the groupconsisting of C₁-C₃₀ alkyl, hydrogen, C₁-C₃₀ alkoxy, and C₁-C₃₀polyoxyalkyl, and wherein if R′ and R″ are both C(O)O—R′″, then at leastone R′″ for either R′ or R″ must be H, and at most one R′″ for either R′or R″ is a metal cation.
 22. The polymer additive composition of claim19, wherein said additive composition is present in a form selected fromthe group consisting of a powder, a pellet, or a liquid, and whereinsaid composition also comprises at least one polymer, and, optionally,at least one compound selected from the group consisting ofplasticizers, acid scavengers, antioxidants, antimicrobials, flameretardants, light stabilizers, antistatic agents, colorants, pigments,and any combination thereof.
 23. The polymer additive composition ofclaim 20, wherein said additive composition is present in a formselected from the group consisting of a powder, a pellet, or a liquid,and wherein said composition also comprises at least one polymer, and,optionally, at least one compound selected from the group consisting ofplasticizers, acid scavengers, antioxidants, antimicrobials, flameretardants, light stabilizers, antistatic agents, colorants, pigments,and any combination thereof.
 24. The polymer additive composition ofclaim 21, wherein said additive composition is present in a formselected from the group consisting of a powder, a pellet, or a liquid,and wherein said composition also comprises at least one polymer, and,optionally, at least one compound selected from the group consisting ofplasticizers, acid scavengers, antioxidants, antimicrobials, flameretardants, light stabilizers, antistatic agents, colorants, pigments,and any combination thereof.
 25. A kit comprising separate materials forintroduction within molten thermoplastic formulations, wherein at leasttwo separate formulations are provided within said kit, wherein a firstformulation comprises at least one organic salt, and wherein a secondformulation comprises at least one compound substantially soluble withinmolten polypropylene selected from the group consisting of at least onebicyclic compound and at least one monocycloaliphatic compound.
 26. Thepolymer additive composition of claim 25 wherein said at least onemonocycloaliphatic compound conforms to the structure of Formula (I):

wherein wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are eitherthe same or different and are individually selected from the groupconsisting of hydrogen, C₁-C₉ alkyl [wherein any two vicinal(neighboring) or geminal (same carbon) alkyl groups may be combined toform a carbocyclic ring of up to six carbon atoms], hydroxy, C₁-C₉alkoxy, C₁-C₉ alkyleneoxy, amine, and C₁-C₉ alkylamine, halogens(fluorine, chlorine, bromine, and iodine), and phenyl, wherein geminalconstituents may be the same except that such geminal constituentscannot simultaneously be hydroxy; and wherein geminal constituents maybe different from each other, except that such geminal constituents maynot be hydroxy and halogen or hydroxy and amine simultaneously.
 27. Thepolymer additive composition of claim 25 wherein said at least onemonocycloaliphatic compound conforms to the structure of Formula (II):

wherein R₁₁, R₁₂, R₁₃, R₁₄ R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, and R₂₀ areindividually selected from the group consisting of hydrogen, C₁-C₉alkyl, hydroxy, C₁-C₉ alkoxy, C₁-C₉ alkyleneoxy, amine, and C₁-C₉alkylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal C₁-C₉carbocyclic, wherein geminal constituents may be the same except thatsuch geminal constituents cannot simultaneously be hydroxy; and whereingeminal constituents may be different from each other, except that suchgeminal constituents may not be hydroxy and halogen or hydroxy and aminesimultaneously; wherein at least one of R′ and R″ is eitherC(O)—NR₂₁C(O) or C(O)O—R′″, wherein R₂₁ is selected from the groupconsisting of C₁-C₃₀ alkyl, hydrogen, C₁-C₃₀ alkoxy, and C₁-C₃₀polyoxyalkyl, and wherein if R′ and R″ are both C(O)O—R′″, then at leastone R′″ for either R′ or R″ must be H, and at most one R′″ for either R′or R″ is a metal cation.
 28. The kit of claim 25, wherein said firstseparate formulation is present in a form selected from the groupconsisting of a powder, a pellet, or a liquid, and wherein saidcomposition also comprises at least one polymer, and, optionally, atleast one compound selected from the group consisting of plasticizers,acid scavengers, antioxidants, antimicrobials, flame retardants, lightstabilizers, antistatic agents, colorants, pigments, and any combinationthereof; and wherein said second separate formulation is present in aform selected from the group consisting of a powder, a pellet, or aliquid, and wherein said composition also comprises at least onepolymer, and, optionally, at least one compound selected from the groupconsisting of plasticizers, acid scavengers, antioxidants,antimicrobials, flame retardants, light stabilizers, antistatic agents,colorants, pigments, and any combination thereof.
 29. The kit of claim26, wherein said first separate formulation is present in a formselected from the group consisting of a powder, a pellet, or a liquid,and wherein said composition also comprises at least one polymer, and,optionally, at least one compound selected from the group consisting ofplasticizers, acid scavengers, antioxidants, antimicrobials, flameretardants, light stabilizers, antistatic agents, colorants, pigments,and any combination thereof; and wherein said second separateformulation is present in a form selected from the group consisting of apowder, a pellet, or a liquid, and wherein said composition alsocomprises at least one polymer, and, optionally, at least one compoundselected from the group consisting of plasticizers, acid scavengers,antioxidants, antimicrobials, flame retardants, light stabilizers,antistatic agents, colorants, pigments, and any combination thereof. 30.The kit of claim 27, wherein said first separate formulation is presentin a form selected from the group consisting of a powder, a pellet, or aliquid, and wherein said composition also comprises at least onepolymer, and, optionally, at least one compound selected from the groupconsisting of plasticizers, acid scavengers, antioxidants,antimicrobials, flame retardants, light stabilizers, antistatic agents,colorants, pigments, and any combination thereof; and wherein saidsecond separate formulation is present in a form selected from the groupconsisting of a powder, a pellet, or a liquid, and wherein saidcomposition also comprises at least one polymer, and, optionally, atleast one compound selected from the group consisting of plasticizers,acid scavengers, antioxidants, antimicrobials, flame retardants, lightstabilizers, antistatic agents, colorants, pigments, and any combinationthereof.
 31. A method of nucleating a thermoplastic formulationcomprising the steps of a) providing a molten thermoplastic formulation;b) introducing, either simultaneously or separately, at least one acidcompound and at least one organic salt; and c) allowing the resultantmixture in step “b” to cool to form a nucleated thermoplastic article;wherein the resultant thermoplastic comprises at most 5% in total partsof beta-crystals of polypropylene; and wherein said nucleatedthermoplastic article exhibits a peak crystallization temperature inexcess of that for the same thermoplastic free from any nucleation agenttherein.